Three new 1,4-anhydro-glucopyranose derivatives having different hydroxyl protective groups such as 1,4-anhydro-2,3,6-tri-O-methyl-alpha-D-glucopyranose (AMGLU), 1,4-anhydro-6-O-benzyl-2,3-di-O-methyl-alpha-D-glucopyranose (A6BMG), and 1,4-anhydro-2,3-di-O-methyl-6-O-trityl-alpha-D-glucopyranose (A6TMG) were synthesized from methyl alpha-D-glucopyranoside in good yields. Their polymerizability was compared with that of 1,4-anhydro-2,3,6-tri-O-benzyl-alpha-D-glucopyranose (ABGLU) reported previously. The tri-methylated monomer, AMGLU, was polymerized by a PFS catalyst to give 1,5-alpha-furanosidic polymer having number-average molecular weights ((M) over bar(n)) in the range of 2.8 x 10(3) to 6.8 x 10(3). The C-13-NMR spectrum was compared with that of methylated amylose and cellulose. Other anhydro monomers, A6BMG and A6TMG, gave the corresponding 1,5-alpha furanosidic polymers having (M) over bar(n) = 17.1 x 10(3) and 1.8 x 10(3), respectively. Thus, the substituents at the C2 and C6 positions were found to play an important role for the ring-opening polymerizability of the 1,4-anhydro-glucose monomers. In addition, debenzylation of the tribenzylated polymer gave free (1 --> 5)-alpha-D-glucofuranan,